Supplement of Technical Note: Emission Factors, Chemical

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Supplement of Atmos. Chem. Phys., 21, 4779–4796, 2021 https://doi.org/10.5194/acp-21-4779-2021-supplement © Author(s) 2021. CC BY 4.0 License.

Supplement of Technical note: Emission factors, chemical composition, and morphology of particles emitted from Euro 5 diesel and gasoline light-duty vehicles during transient cycles

Evangelia Kostenidou et al.

Correspondence to: Evangelia Kostenidou ([email protected]) and Barbara D’Anna ([email protected])

The copyright of individual parts of the supplement might differ from the article licence. -1 Table S1. EF of regulated gas phase species: CO2 in g km , CO, THC and NOx in mg km-1.

Artemis WLTC Cold Urban Hot Urban Motorway Cold Start Hot Start GDI1 CO2 221±11 197±5 151±5 CO 104±47 5±0.5 326±207 NOx 110±44 102±6 30±23 THC 45±20 0.8±0.3 2.1±0.9 GDI2 CO2 150±31 129±17 CO 694±821 308±329 NOx 1217±498 1387±526 THC 112±116 73±112

GDI3 CO2 191±5 173±7 130±2 CO 714±228 557±561 586±206

NOx 153±60 30±12 9±3 THC 219±0.4 25±14 8±2

PFI CO2 155±2 112±2 CO 106±16 112±2

NOx 69±13 7±1 THC 5.5±0.4 2.0±0.3 D1 CO2 168±18 147±7 144±14 CO 453±208 95±44 3±1.6 NOx 697±120 741±112 890±233 THC 57±20 30±3 1.7±2 D2 CO2 120±1.5 116±1.8 CO 54±11 27±7.5 NOx 240±25 232±32 THC 14.7±3 12.4±2.5

D3 CO2 210±4 142±0.1 CO 601±45 9±0.2

NOx 396±8 510±160 THC 91±28 10±1

Table S2. PAHs identified in diesel and gasoline Euro 5 vehicles emissions. They have been classified as unsubstituted PAHs (UnSubPAHs), methylated PAHs (MPAHs), oxygenated PAHs (OPAHs), nitro-substituted derivatives (NPAHs) and amino PAHs (APAHs).

Group Compound Molecular m/z formula UnSubPAH Naphthalene C10H8 128 Acenaphthylene C12H8 152 Acenaphthene C12H10 154 Fluorene C13H10 166 Paracyclene C14H8 176 Anthracene/ C14H10 178 Phenanthrene Benzo[def]fluorene C15H10 190 Pyrene/ C16H10 202 Fluoranthene/ Acephenanthrylene Benzofluorene C17H12 216 Benz[a]anthracene/ C18H12 228 Triphenylene/ Chrysene Corannulene/ C20H10 250 Dicyclopenta[cd,mn]pyrene Benzo[b]fluoranthene/ C20H12 252 Benzo[j]fluoranthene/ Benzo[k]fluoranthene/ Benzo[a]pyrene/ Benzo[e]pyrene Indio[1,2,3-cd]pyrene/ C22H12 276 Benzo[ghi]perylene Dibenzanthracene/ C22H14 278 Pentacene 1H- C23H12 288 Benzo[ghi]cyclopenta[pqr]perylene MPAH Methyl-naphthalene C11H10 142 Dimethyl-naphthalene C12H12 156 Methyl-acenaphthene C13H12 168 Methyl-fluorene C14H12 180 Methyl-phenanthrene C15H12 192 Dimethyl-fluorene C15H14 194 Ethyl-phenanthrene C16H14 206 Trimethyl-phenanthrene C17H16 220 Retene/ C18H18 234 Tetramethyl phenanthrene Methylbenzo[ghi]fluoranthene C19H12 240 Methylbenz[a]anthracene/ C19H14 242 methyl chrysene Di-methylbenz(a)anthracene C20H16 256 Methyl cholanthrene C21H16 268 OPAH Indanone C9H8O 132 Benzocycloheptenone C11H8O 156 Naphthoquinone C10H6O2 158 Dibenzofuran C12H8O 168 Fluorenone C13H8O 180 Dibenzopyran C13H10O 182 Hydroxydibenzofuran C12H8O2 184

Table S2. PAHS identified in diesel and gasoline Euro 5 vehicles emissions. They have been classified as unsubstituted PAHs (UnSubPAHs), methylated PAHs (MPAHs), oxygenated PAHs (OPAHs), nitrogen-substituted derivatives (NPAHs) and amino PAHs (APAHs) (continued).

Family Compound Molecular m/z formula OPAH Anthrone C14H10O 194 Xanthone C13H8O2 196 Cyclcopenta-phenanthrene-one C15H8O 204 Aceanthraquinone C16H8O2 232 Benzo[cd]pyrenone C19H10O 254 NPAH Nitro-anthracene/ C14H9NO2 223 Nitro-phenanthrene Dinitrofluorene C13H8N2O4 256 APAH Aminopyrene/ C16H11N 217 Carbazole Aminobenzanthrone C18H13NO 259 Dibenzocarbazole C20H13N 267 Amino benzopyrene

Table S3. Intercomparison of PAHs mass concentration (ng m-3) measured from the extract of one quartz filter (GC-MS analysis) and on-line AMS measurements for the emission of the GDI3 vehicle.

Molecular Compound Concentration (ng m-3) 3 cycles weight (1 urban hot + 2 motorway)

GC-MS HR-ToF-MS 128 Naphthalene 45 245 178 Phenanthrene*/Anthracene 100 453 202 Pyrene/Fluoranthene*/Acephenanthrylene 111 480 228 Benzo[a]anthracène/Chrysène 25 69 252 Benzo[b]fluoranthene/Benzo[j]fluoranthene 77 34 / Benzo[k]fluoranthene*/Benzo[a]pyrene/* Benzo[e]pyrene/Perylene 276 Indéno[123cd]pyrène/Benzo[ghi]perylène 31 25 142 Methyl-naphthalene* 27 80 180 Methyl-fluorene 24 53 168 Dibenzofuran 26 28 180 Fluorenone 76 75 208 Anthraquinone* 26 28 * compounds used for PAHs calibration and quantification during GC-MS analysis.

Table S4. Fraction (%) of major PAHs emitted from the GDI3, PFI and D3 vehicles during Artemis driving cycles: Cold Urban (CU) and Motorway (MW).

Compound GDI3 PFI D3 CU MW CU MW CU MW UnsPAHs Naphthalene 10.3 9.6 14.3 13.6 16.9 19.1 Acenaphthylene 4.3 7.8 4.5 5.4 8.3 9.7 Acenaphthene 2.4 3.6 2.0 2.6 4.2 5.2 Fluorene 1.9 2.5 2.2 3.2 5.0 4.3 Anthracene/Phenanthrene 5.3 15.9 4.1 8.9 6.9 8.2 Pyrene/Fluoranthene/Acephenanthrylene 5.9 13.7 3.3 5.8 2.1 1.9 Benz[a]anthracene/Triphenylene/Chrysene 2.2 1.6 1.7 1.0 1.3 0.7 Paracylene 1.7 3.5 1.0 1.2 2.1 2.8 Benzo[def]fluorene 1.4 1.5 1.1 1.9 3.4 2.1 Benzo[a, e]pyrene/Benzo[b,j,k]fluoranthene 2.3 1.1 3.8 0.6 0.7 0.4 Cyclopenta[cd]pyrene/Benzo[ghi]fluoranthene 3.3 2.0 2.5 1.2 1.6 1.0 Dibenzoanthracene/Pentacene 0.5 0.2 1.5 0.8 0.2 0.1 Indio[1,2,3-cd]pyrene/Benzo[ghi]perylene 3.0 0.6 6.6 0.7 0.4 0.3 Coronene 1.9 0.3 5.3 0.6 0.1 0.1 MPAHs Methyl-naphthalene 3.4 2.9 4.6 4.4 7.6 8.2 Dimethyl-naphthalene 1.9 1.9 2.6 2.9 5.4 5.5 Methyl-acenaphthene 1.3 1.7 1.3 2.4 3.3 3.3 Methyl-fluorene 1.1 2.1 1.0 2.1 3.4 2.9 Methyl-phenanthrene 0.7 2.3 1.1 1.7 4.7 3.1 Ethyl-phenanthrene 1.3 1.3 1.0 2.2 3.8 2.3

OPAHs Indanone 2.4 1.8 0.9 1.2 0.4 0.9 Anthraquinone 2.2 0.9 3.9 8.7 2.6 3.9 Dibenzofuran 1.0 1.0 0.7 1.3 0.5 1.6 Fluorenone 1.6 2.7 1.1 2.0 0.3 3.1 Dibenzopyran 1.5 1.1 1.3 2.4 0.3 0.4 Benzo[cd]pyrenone 1.4 0.6 0.8 0.5 0.1 0.1

NPAHs Nitro-fluorene 0.9 0.1 0.8 0.4 0.5 0.2 Nitro-anthracene/Nitro-phenanthrene 8.1 8.6 0.9 1.2 0.1 0.1 Nitro-pyrene 0.5 0.1 0.8 0.2 0.1 0.03 Nitrochrysene 0.4 0.03 0.7 0.2 0.06 0.04

APAHs Aminopyrene/Carbazole 0.8 0.6 0.5 0.6 1.5 0.5 Dibenzocarbazole/Amino benzopyrene 5.3 0.4 2.4 3.5 0.3 0.2 Dibenz[a,j]acridine 0.1 0.03 1.1 1.2 0.2 0.2

Table S5. Major inorganic species found in fresh and used lubricant oil, TAE diesel and gasoline fuels (analysis by ICP-MS). Other elements such as Cr, Ni, Al and Mg were found in concentration below 3 ppm.

Old Old Diesel Fresh lubricant lubricant TAE 85 Gasoline lubricant oil oil Fuel Fuel oil (Diesel) (Gasoline) Sulphur 0.14wt % 0.14wt% 0.12wt% 16 ppm 34 ppm Calcium (ppm) 1630 1441 1829 ≤ 3 ≤ 5 Phosphor (ppm) 638 614 709 ≤ 3 ≤ 5 Zinc (ppm) 849 728 857 ≤ 3 ≤ 5 Iron (ppm) ≤ 3 66 75 ≤ 2 ≤ 5 Silicium (ppm) 5 15 11 31 138 Molybdenum (ppm) ≤ 3 94 ≤ 5 ≤ 3 ≤ 5 Copper (ppm) ≤ 3 16 7 ≤ 3 ≤ 5

Table S6. EF for all gasoline and diesel vehicles and for all tested conditions. All values are expressed in µg km-1. BDL stands for Below Detection Limit.

Vehicle Species Artemis WLTC Cold Urban Hot Motorway Cold Start Hot Start Urban GDI1 BC 7140±500 960±190 1990±810 GDI2 BC 5700±800 230±60 Organics 103.5±52.23 41.23±8.38 Sulphate BDL BDL Ammonium BDL BDL Nitrate 7.12±3.98 5.08±2.96 GDI3 BC 3180±137 200±160 767±330 Organics 66.3±64.8 5.34±4.42 25.3±13.5 PAHs 1.54±0.81 0.13±0.01 1.10±0.73 Sulphate 0.34±0.07 0.06±0.03 0.06±0.04 Ammonium 0.28±0.04 0.02±0.01 0.09±0.08 Nitrate 1.31±0.41 0.12±0.09 0.48±0.43 PFI BC 135.25±8.15 NA 22.27±11.23 Organics 8.40±3.70 NA 1.00±0.26 PAHs 0.43±0.16 NA 0.04±0.05 Sulphate 0.28±0.11 NA 0.04±0.03 Ammonium 0.24±0.14 NA 0.03±0.01 Nitrate 0.88±0.45 NA 0.03±0.01 D1 BC 76.0±55.0 8.0±4.0 9.0±3.9 Organics 11.0±0.81 0.15±0.05 1.91±1.32 Sulphate BDL BDL 1.34±1.26 Ammonium BDL BDL 0.38±0.21 Nitrate 0.28±0.02 0.18±0.06 0.18±0.09 D2 BC 8.0±4.0 3.0±1.0 Organics 0.74±0.25 0.28±0.01 Sulphate 4.19±3.20 0.28±0.05 Ammonium 0.68±0.53 0.06±0.02 Nitrate 0.14±0.09 0.03±0.01 D3 BC 378.38±136.59 NA 927.72±139.16 Organics 61.0±38.2 NA 65.7±36.4 PAHs 2.04±0.19 NA 1.73±0.95 Sulphate 0.18±0.06 NA 0.22±0.13 Ammonium 0.15±0.01 NA 0.15±0.06 Nitrate 0.25±0.05 NA 0.82±0.53

Table S7. Fuel consumption (l km-1) and fuel densities (kg l-1).

Vehicle Fuel Consumption Fuel density Cold Urban Motorway GDI1 0.733 0.096 0.063

Cold start WLTC Hot start WLTC GDI2 0.733 0.064 0.059 Cold Urban Motorway GDI3 0.733 0.085 0.077 Cold Urban Motorway PFI 0.733 0.068 0.048 Cold Urban Motorway D1 0.840 0.063 0.051 Cold start WLTC Hot start WLTC D2 0.840 0.044 0.047 Cold Urban Motorway D3 0.840 0.077 0.051

7 2.5 (a) C10H8 (Naphthalene) (b) C11H10 (Methyl-naphthalene) 6 2.0 5 4 1.5

C8H14O2 3

C H O 1.0 Diff, Hz/ns Diff, 7 12 2 Diff, Hz/ns C6H6O4 2 C10H22 0.5 1 0 0.0 128.00 128.10 128.20 141.90 142.00 142.10 142.20 142.30 m/z m/z 12 (d) C14H9NO2 (Nitro-antracene) 10

C14H11N2O

Diff, Hz/ns 4

2 H2ClN3O7S

0 222.80 222.90 223.00 223.10 223.20 m/z Figure S1. Examples of HR-AMS fitting for (a) naphthalene (C10H8) at m/z 128, (b) methyl-naphthalene (C11H10) at m/z 142, (c) anthracene/phenanthrene (C14H10) at m/z 178 and (d) Nitro-anthracene (C14H9NO2) at m/z 223.

3 14 3000 160 13 2500 Cold Start Organics 120 x10 12 2000 Black Carbon 11 1500 100 120 10 1000 Nitrate m (µg concentration mass Nitrate 80

) 300

) -3 -3 1200 60 80 200 800 40

Speed(Km/h) 40 100 400 20 0 0 0 0 600 400 Hot Start 120 120 300 400 80 80

200

-3 ) BCconcentration mass (µg m 200 40

100 40 Organicconcentration mass (µg m

0 0 0 0 0 500 1000 1500 Time (sec)

Figure S2. Time series of organics, nitrate and BC for WLTC cycle cold start (upper plot) and hot start (lower plot) for the GDI2 vehicle.

Sulphate Organics Ammonium

Speed Nitrate m (μg concentration mass Ammonium Nitrate, Sulphate, 250

Cold Urban 60 )

-3 200 12 50 150 40 8 30 100 (Km/h) Speed 20 4 50 10 0 0 0 30 Motorway 150 1.0 0.8 20 100 0.6

Organicmass concentration (μg m 0.4 10 50 0.2

0 0 0.0 -3

0 250 500 750 1000 )

Time (sec) Figure S3. Time series of organics, sulphate, nitrate and ammonium for Artemis cold urban (upper) and motorway cycles (lower) for the PFI vehicle. BC measurements are not available for this vehicle.

From Excel sent in December

100 Cold Start Organics 120 80 Sulphate

) 60 Ammonium 80 -3 40 40

20 Speed (Km/h) Speed 0 0 8 Hot Start 120 6 80 4

Massconcentration (µg m 40 2

0 0 0 500 1000 1500 Time (sec)

Figure S4. Time series of organics, sulphate and ammonium for WLTC cold start (upper) and hot start (lower) for the D2 vehicle.

Sulphate

Organics m (μg concentration mass Ammonium Nitrate, Sulphate, Ammonium Speed Nitrate 250 Cold Urban 60 10 200

) 50 8 -3 150 40 6 30 100 (Km/h) Speed 4 20 50 10 2 0 0 0 10 300 Motorway 150 8 200 100 6 4 100 50

Organicmass concentration (μg m 2 0 0 0

0 250 500 750 1000 -3 ) Time (sec) Figure S5. Time series of organics, sulphate, nitrate and ammonium for Artemis cold urban cycle (upper) and a motorway (lower) for the D3 vehicle.

Figure S6. AMS HR spectra speciation for organic fragments for the PFI vehicle (ARTEMIS cycle).

WLTC

Cold start Hot Start

0.20 45

41 min 5 first 55 0.15 41 43 0.10 57 55 57 0.05 69 71 69 97 97 0.00

0.20 last 5 min 5 last 0.15 43 41 55 41 43

0.10 57 57 Fractionof OrganicSignal 55 69 0.05 71 69 71

0.00 40 80 120 40 80 120 m/z

Figure S7. AMS UMR spectra for organic fragments for the GDI2 vehicle (WLTC).

0.14 43 0.12 41 0.10 55 0.08 57

0.06 69 0.04 71

0.02 Fractionof OrganicSignal 0.00 20 40 60 80 100 120 140 m/z Figure S8. UMR mass spectrum for taken at the beginning of a motorway cycle (2 first minutes) for the D1 vehicle.

Figure S9. TEM images of samples collected during hot cycles: (a-c) GDI1 sampling the first 120 sec of the motorway cycle, dilution ratio 40; (d-f) GDI2 sampling the last 120 sec of a WLTC cycle, dilution ratio 46; (g-i) D1 vehicle sampling first 300 sec of the motorway cycle, dilution ratio 40.

Figure S10. XPS spectra of particles collected from the PFI vehicle: (a) survey spectrum and elemental composition (table in insert); (b) deconvolution of the C1s spectrum; (c) deconvolution of the O1s spectrum.